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WO2013002157A1 - Matériau composite à base de carbone contenant du silicium dans lequel des particules fines d'alliage au silicium ou de métal au silicium revêtues de lithium sont dispersées - Google Patents

Matériau composite à base de carbone contenant du silicium dans lequel des particules fines d'alliage au silicium ou de métal au silicium revêtues de lithium sont dispersées Download PDF

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WO2013002157A1
WO2013002157A1 PCT/JP2012/066098 JP2012066098W WO2013002157A1 WO 2013002157 A1 WO2013002157 A1 WO 2013002157A1 JP 2012066098 W JP2012066098 W JP 2012066098W WO 2013002157 A1 WO2013002157 A1 WO 2013002157A1
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silicon
group
lithium
fine powder
composite material
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Japanese (ja)
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志成 張原
日野　賢一
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DuPont Toray Specialty Materials KK
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Dow Corning Toray Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/06—Metal silicides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a silicon-containing carbon-based composite material, an electrode active material composed of the composite material, an electrode including the active material, and an electricity storage device including the electrode.
  • An electricity storage device in particular, a lithium or lithium ion secondary battery has been studied as a kind of high energy density type secondary battery.
  • a negative electrode material for such a lithium ion secondary battery it has been reported many times that a silicon-containing carbon material obtained by thermally decomposing a silicon polymer is used.
  • materials that can be used for manufacturing a large-capacity battery by using polysilane and coal tar pitch as precursors are disclosed. The production is described. JP-A-10-74506, JP-A-10-275617, JP-A-2004-273377, and J. Org. Electrochem. Soc.
  • a high-capacity battery is obtained by thermally decomposing a siloxane polymer and then introducing lithium into an electrode for a lithium or lithium ion secondary battery.
  • a lithium or lithium ion secondary battery equipped with an electrode containing such a silicon-containing carbon material has high reversible capacity, but has low initial charge / discharge efficiency, and lacks practical performance in terms of charge / discharge cycle characteristics, etc. is doing.
  • Japanese Patent Laid-Open No. 11-96993 describes that the initial irreversible capacity is reduced by coating an inorganic solid electrolyte containing lithium on the surface of a negative electrode active material such as graphite, silicon, and tin-based oxide.
  • a negative electrode active material such as graphite, silicon, and tin-based oxide.
  • Japanese Patent Laid-Open No. 2006-179305 discloses that a layer containing LiF + and Li 2 OH + is formed on the surface of a negative electrode having a negative electrode active material containing silicon or tin to suppress the decomposition reaction of the electrolytic solution. To improve cycle characteristics.
  • JP 2007-66726 A an active material powder containing silicon or a silicon alloy, a mixture layer containing a binder and lithium oxide is disposed on a current collector and heat-treated, thereby generating gas during high-temperature storage. It is described that the charge / discharge cycle characteristics are enhanced while suppressing the above.
  • Japanese Patent Application Laid-Open No. 2005-310759 describes a composite in which metal silicon or metal silicon alloy powder is dispersed in a silicon-containing carbon-based composite powder.
  • a lithium or lithium ion secondary battery provided with an electrode containing such a composite as an active material has insufficient charge capacity, charge / discharge efficiency, or capacity maintenance rate upon repeated charge / discharge, and is still practical. The level has not been reached.
  • JP 10-97853 A JP-A-10-74506 Japanese Patent Laid-Open No. 10-275617 JP 2004-273377 A JP-A-11-96993 JP 2006-179305 A JP 2007-66726 A JP 2005-310759 A
  • An object of the present invention is to provide a power storage device, in particular, a composite material suitable for an electrode of a lithium or lithium ion secondary battery, an electrode active material composed of the composite material, an electrode using the active material, and a power storage device including the electrode Is to provide.
  • the object of the present invention is achieved by a composite material in which metal silicon or silicon alloy fine powder having a lithium-containing layer on its surface is dispersed in a silicon-containing carbon-based composite material.
  • the average particle diameter of the metal silicon or silicon alloy fine powder is preferably 10 nm to 10 ⁇ m.
  • the lithium content is preferably 0.1 to 10% by mass of the metal silicon or silicon alloy fine powder provided with the lithium-containing layer. When the lithium content is within this range, good conductivity and battery capacity can be maintained.
  • the composite material includes a first step of obtaining a lithium-coated metal silicon or silicon alloy fine powder by forming a lithium-containing layer on the surface of the metal silicon or silicon alloy fine powder, and the lithium-coated metal silicon or silicon alloy fine powder.
  • a crosslinkable group-containing organic compound and (B) the crosslinkable group-containing organic compound are mixed with a crosslinkable silicon-containing compound, and a cured product is obtained by cross-linking the components (A) and (B). It can be obtained by the second step and the third step of heat-treating the cured product.
  • the present invention provides a first step of obtaining a lithium-coated metal silicon or silicon alloy fine powder by forming a lithium-containing layer on the surface of the metal silicon or silicon alloy fine powder, and the lithium-coated metal silicon or silicon alloy fine powder.
  • (A) a crosslinkable group-containing organic compound and (B) the crosslinkable group-containing organic compound are mixed with a crosslinkable silicon-containing compound, and (C) the component (A) and the component (B) are subjected to a crosslinking reaction to obtain a cured product. It has a side as a manufacturing method of a composite material characterized by including the 2nd process obtained and the 3rd process of heat-treating the hardened material.
  • the composite material of the present invention also includes a first step of obtaining a lithium-coated metal silicon or silicon alloy fine powder by forming a lithium-containing layer on the surface of metal silicon or silicon alloy fine powder, and (A) a crosslinkable group-containing organic material.
  • a second step of obtaining a cured product by crosslinking reaction of the compound and (B) a silicon-containing compound capable of crosslinking the crosslinkable group-containing organic compound, and the lithium-coated metal silicon or silicon alloy fine powder and the cured product are machined
  • a third step of mixing, combining, and heat-treating while applying a target energy is
  • the composite material of the present invention includes a first step of obtaining a lithium-coated metal silicon or silicon alloy fine powder by forming a lithium-containing layer on the surface of metal silicon or silicon alloy fine powder, and (A) containing a crosslinkable group A second step of obtaining a cured product by crosslinking reaction of an organic compound and (B) a silicon-containing compound capable of crosslinking the crosslinkable group-containing organic compound, and heat-treating the cured product to obtain a silicon-containing carbon-based composite material And a fourth step in which the lithium-coated metal silicon or silicon alloy fine powder and the silicon-containing carbon-based composite material are mixed and compounded while applying mechanical energy.
  • Examples of the step of obtaining lithium-coated metal silicon or silicon alloy fine powder include a method in which metal silicon or silicon alloy fine powder and lithium or lithium compound are mixed and heat-treated.
  • lithium compound examples include LiOH (LiOH.H 2 O), Li 2 O, LiR (R is an alkyl group or an organosiloxy group), LiOR (R is the same as described above), LiCO 3 , LiNO 3 , LiX (X is fluorine, halogen atom such as chlorine), Li complex compound, (R is same as defined above, n represents the number of 1 ⁇ 3) R n Si ( OLi) 4-n are illustrated.
  • the electrode active material of the present invention is composed of the above composite material.
  • the electrode of the present invention contains the above electrode active material.
  • the said electrode can be used conveniently for an electrical storage device, especially a lithium or lithium ion secondary battery.
  • the composite material of the present invention has a high initial discharge capacity and an initial irreversible capacity (difference between the initial charge capacity and the initial discharge capacity) is reduced, the power storage device, particularly lithium or lithium ion secondary battery Suitable for electrodes. Further, the composite material of the present invention can be manufactured by a simple manufacturing process using inexpensive raw materials.
  • the electrode active material of the present invention is suitable for an electricity storage device, particularly an electrode of a lithium or lithium ion secondary battery.
  • the electrode of the present invention can impart a high initial charge / discharge capacity and stable charge / discharge cycle characteristics to the battery.
  • the electrical storage device of this invention can have a high initial charging / discharging capacity
  • the lithium ion secondary battery which is an example of the electrical storage device of this invention is shown.
  • the lithium secondary battery which is an example of the electrical storage device of this invention is shown.
  • the composite material of the present invention includes a first step of forming a lithium-containing layer on the surface of metal silicon or silicon alloy fine powder to obtain lithium-coated metal silicon or silicon alloy fine powder, and the lithium-coated metal silicon or silicon alloy fine powder.
  • the powder is mixed with (A) a crosslinkable group-containing organic compound and (B) the crosslinkable group-containing organic compound with a crosslinkable silicon-containing compound, and (A) component and (B) component are subjected to a cross-linking reaction to obtain a cured product.
  • the manufacturing method of the composite material of this invention is not limited to the said method,
  • the lithium containing metal silicon or silicon alloy fine powder is obtained by forming a lithium containing layer on the surface of metal silicon or silicon alloy fine powder.
  • the composite material of the present invention can also be obtained by the third step in which the silicon alloy fine powder and the cured product are mixed, combined, and heat-treated while applying mechanical energy.
  • the lithium-coated metal silicon or silicon alloy fine powder and the silicon-containing carbon-based composite material may be mixed and composited while applying mechanical energy.
  • metal silicon or silicon alloy fine powder high purity metal silicon for semiconductors, powder obtained by pulverizing chemical silicon metal, silicon metal powder obtained by pulverizing the above silicon metal by a rapid cooling method, obtained from thermal decomposition of silane gas
  • the obtained amorphous silicon metal powder, metal silicon or silicon alloy fine powder prepared by reduction of chlorosilane gas can be used.
  • Examples of the silicon alloy fine powder include alloys of silicon and iron, copper, aluminum, manganese, and magnesium, and more specifically, SiAl, SiMn, SiMg, SiGe, Al-Si-Mg, and Al-Si. -Mn, Al-Si-Zn, Al-Si-Cu, Ni-Si-Al, Au 1-x Si x, CaSi, CaBaSi, Fe-Si-W is exemplified.
  • lithium compound examples include LiOH (LiOH.H 2 O), Li 2 O, LiR (R is an alkyl group or an organosiloxy group), LiOR (R is the same as described above), LiCO 3 , LiNO 3 , LiX (X is fluorine, halogen atom such as chlorine), Li complex compound, (R is same as defined above, n represents the number of 1 ⁇ 3) R n Si ( OLi) 4-n are illustrated.
  • lithium-containing layer When using a metal silicon fine powder having a silicon oxide film, it is preferable to form a lithium-containing layer using Li metal or surface-treated Li metal.
  • a metal silicon or silicon alloy fine powder having an average particle diameter of 10 nm to 10 ⁇ m is added to a solution obtained by dissolving a lithium compound in a solvent, and the mixture is stirred in a nitrogen atmosphere and then dried. By doing so, lithium-coated metal silicon or silicon alloy fine powder can be obtained.
  • lithium-coated metal silicon or silicon alloy fine powder can be obtained by adding a lithium compound to metal silicon or silicon alloy fine powder, and mixing and stirring while applying mechanical energy.
  • the pulverization, mixing, or surface treatment may be a dry method or a wet method.
  • the crushing device examples include a device that crushes by pressure and striking force: for example, jaw crusher, gyratory crusher, roll crusher, roll mill, automatic mortar, etc .; a striking plate is fixed around the rotor rotating at high speed, and the rotor and striking plate Equipment that pulverizes processed material by shearing force etc .: For example, hammer mill, impact crusher, pin mill, atomizer, pulverizer, etc .; device that rotates while a roll or ball is pressed on the ring, and pulverizes the processed material between them : For example, a ring roller mill, a ring ball mill, a centrifugal roller mill, a ball bearing mill, an ang mill, etc .; a cylindrical crushing chamber is provided, and processing is performed by rotating or vibrating a ball or rod as a crushing medium in the crushing chamber Crushing to crush things Place: For example, a pot mill, a ball mill, a vibration mill, a planetary ball mill, etc .; a
  • a mixing device for example, a mixer having a stirring shaft inside a mixing tank, and a stirring blade attached to the shaft to mix powders: for example, a super mixer, a high speed mixer, a Henschel mixer, etc .; powder Consisting of a vertical cylinder with an inlet and a main shaft with a mixing blade, the main shaft is supported by an upper bearing and the discharge side is free: a continuous mixer such as a flexomix mixer; A continuous mixer in which a raw material is introduced into the upper part of the disk, and the disk is rotated at a high speed and mixed by a shearing action: for example, a flow jet mixer, a spiral pin mixer and the like.
  • Examples of the surface treatment apparatus include a hybridizer manufactured by Nara Machinery Co., Ltd., a mechano-fusion, a nobilta manufactured by Hosokawa Micron Corporation, and the like.
  • the mixing agitation method and apparatus as described above are also applied to the step of mixing and compounding lithium-coated metal silicon or silicon alloy fine powder and cured product or silicon-containing carbon-based composite material while applying mechanical energy. Can be used.
  • the lithium-coated metal silicon or silicon alloy fine powder obtained as described above is preferably further heat-treated.
  • the heat treatment temperature is not particularly limited, but is generally 200 ° C. to 800 ° C.
  • the lithium-containing layer on the surface of the metal silicon or silicon alloy fine powder preferably has a thickness of 5 nm to 500 nm.
  • the lithium atom content is preferably 0.1 to 10% by mass of the entire lithium-coated metal silicon or silicon alloy fine powder.
  • Such a lithium-coated metal silicon or silicon alloy fine powder is obtained, for example, in the step of forming a lithium-containing layer on the surface of the metal silicon or silicon alloy fine powder, It can be obtained by adjusting to 0.1 to 10% by mass of the entire silicon alloy fine powder.
  • a lithium-containing layer bonded to silicon atoms can be obtained by the following reaction.
  • 2Si + 2LiOH 2 ⁇ SiOLi + H 2
  • the crosslinkable group in the component (A) is not particularly limited as long as it is a crosslinkable group.
  • an aliphatic unsaturated group, an epoxy group, an acrylic group, a methacryl group, an amino group, a hydroxyl group, A mercapto group or a halogenated alkyl group may be mentioned.
  • Specific examples of the aliphatic unsaturated group include alkenyl groups such as vinyl group, propenyl group, butenyl group, pentenyl group and hexenyl group; and alkynyl groups such as acetyl group, propynyl group and pentynyl group.
  • the epoxy group examples include a glycidyl group, a glycidoxy group, an epoxycyclohexyl group, a 3-glycidoxypropyl group, and a 2- (3,4-epoxycyclohexyl) ethyl group.
  • Specific examples of the acryl group include a 3-acryloxypropyl group.
  • Specific examples of the methacryl group include a 3-methacryloxypropyl group.
  • Specific examples of the amino group include a 3-aminopropyl group and an N- (2-aminoethyl) -3-aminopropyl group.
  • hydroxyl group examples include hydroxyalkyl groups such as hydroxyethyl group and hydroxypropyl group; and hydroxyaryl groups such as hydroxyphenyl group.
  • mercapto group examples include a 3-mercaptopropyl group.
  • halogenated alkyl group examples include a 3-chloropropyl group.
  • the component (A) may be a mixture of an organic compound having one crosslinkable group in one molecule and an organic compound having at least two crosslinkable groups in one molecule.
  • the content of the latter in the mixture is not particularly limited, but is preferably at least 15 mass (weight)%, and more preferably at least 30 mass (weight)% because of its excellent crosslinkability. preferable.
  • the component (A) may not contain a silicon atom or may contain a silicon atom.
  • the component (A) that does not contain a silicon atom is preferably an organic compound having at least one aromatic ring in the molecule from the viewpoint of good carbonization efficiency by heat, such as easy formation of a graphene structure.
  • component (A) specifically, an aliphatic hydrocarbon compound containing no silicon atom having a crosslinkable group at the molecular chain terminal and / or molecular chain side chain, the molecular chain terminal and / or molecular chain side
  • Examples include aromatic hydrocarbon compounds that do not contain silicon atoms, and alicyclic compounds that contain a crosslinkable group in the molecule and that do not contain silicon atoms that have hetero atoms other than carbon atoms such as nitrogen atoms, oxygen atoms, and boron atoms. Is done.
  • R 1 is a crosslinkable group, and examples thereof include an aliphatic unsaturated group, an epoxy group, an acrylic group, a methacryl group, an amino group, a hydroxyl group, a mercapto group, and a halogenated alkyl group. Is exemplified by the same groups as described above, wherein m and n are each an integer of 1 or more, and
  • R 1 is a crosslinkable group, and examples thereof are the same groups as described above.
  • x is an integer of 1 or more.
  • R 2 represents an x-valent aromatic group. That is, in the formula, when x is 1, R 2 represents a monovalent aromatic group, and specific examples thereof include the following groups.
  • aromatic hydrocarbon compounds include ⁇ - or ⁇ -methylstyrene, ⁇ - or ⁇ -ethylstyrene, methoxystyrene, phenylstyrene, chlorostyrene, o-, m- or p-methylstyrene.
  • Ethyl styrene methyl silyl styrene, hydroxy styrene, cyano styrene, nitro styrene, amino styrene, carboxy styrene, sulfoxy styrene, sodium styrene sulfonate, vinyl pyridine, vinyl thiophene, vinyl pyrrolidone, vinyl naphthalene, vinyl anthracene, vinyl biphenyl Is exemplified.
  • R 2 represents a divalent aromatic group, and specific examples thereof include the following groups.
  • aromatic hydrocarbon compounds include divinylbenzene, divinylbiphenyl, vinylbenzyl chloride, divinylpyridine, divinylthiophene, divinylpyrrolidone, divinylnaphthalene, divinylxylene, divinylethylbenzene, and divinylanthracene.
  • the aromatic hydrocarbon compound is preferably divinylbenzene because the resulting cured product has excellent thermal decomposition characteristics.
  • R 2 represents a trivalent aromatic group, and specific examples thereof include the following groups.
  • aromatic hydrocarbon compounds include trivinylbenzene and trivinylnaphthalene.
  • R 1 is a crosslinkable group, and examples thereof are the same groups as described above.
  • R 1 is a crosslinkable group, and examples thereof are the same groups as described above.
  • the component (A) containing a silicon atom is not particularly limited as long as it has a crosslinkable group, and examples thereof include a monomer, oligomer or polymer containing a silicon atom.
  • a silane composed of a structural unit characterized by having a silicon-silicon bond a silazane composed of a structural unit characterized by having a silicon-nitrogen-silicon bond, and a silicon-oxygen-silicon bond
  • Examples thereof include siloxanes composed of structural units, carbosilanes composed of structural units characterized by having a silicon-carbon-silicon bond, and mixtures thereof.
  • Examples of the silane of the component (A) include an average unit formula: R 3 4 Si Or average unit formula: (R 3 3 Si) a (R 3 2 Si) b (R 3 Si) c (Si) d (In the formula, each R 3 independently represents a crosslinkable group, a monovalent substituted or unsubstituted saturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, or a hydrogen atom.
  • the saturated aliphatic hydrocarbon group is preferably an alkyl group, and the aromatic hydrocarbon group is preferably an aryl group or an aralkyl group.
  • the alkyl group is preferably a C 1 -C 12 alkyl group, C 1 -C 6 alkyl is more preferable.
  • the alkyl group is a linear or branched alkyl group, a cycloalkyl group, or a cycloalkylene group (a linear or branched alkylene group (preferably a C 1 -C 6 alkylene group such as a methylene group or an ethylene group). ) And a carbon ring (preferably an alkyl group composed of a C 3 -C 8 ring).
  • linear or branched alkyl group a linear or branched C 1 -C 6 alkyl group is preferable.
  • the cycloalkyl group is preferably a C 4 -C 6 alkyl group, for example, a cyclobutyl group, a cyclopentyl group, cyclohexyl group, etc., a cyclopentyl group and cyclohexyl group are preferable.
  • the aryl group is preferably C 6 -C 12 aryl, phenyl group, naphthyl group, tolyl group.
  • a C 7 -C 12 aralkyl group is preferable.
  • Examples of the C 7 -C 12 aralkyl group include a benzyl group, a phenethyl group, and phenylpropyl.
  • the hydrocarbon group may have a substituent.
  • substituents include halogens such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; methoxy group, ethoxy group, n-propoxy group, iso C 1 -C 6 alkoxy groups such as propoxy group; amino group; amide group; nitro group; epoxy group and the like.
  • the substituent can be bonded to any part of the hydrocarbon chain, saturated ring or aromatic ring.
  • alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the silane can be prepared using various known methods. For example, a method of dehalogenating a halosilane in the presence of an alkali metal (Macromolecules, 23, 3423 (1990), etc.), a method of anionic polymerization of disilene (Macromolecules, 23, 4494 (1990), etc.), electrode reduction, etc. (J. Chem. Soc., Chem. Commun., 1161 (1990), J. Chem. Soc., Chem. Commun., 897 (1992), etc.), magnesium, etc.
  • a method of dehalogenating a halosilane in the presence of an alkali metal Mocromolecules, 23, 3423 (1990), etc.
  • a method of anionic polymerization of disilene Mocromolecules, 23, 4494 (1990), etc.
  • electrode reduction etc.
  • a method of performing a dehalogenation reaction of halosilanes in the presence of hydrogen (WO98 / 29476, etc.), a method of performing a dehydrogenation reaction of hydrosilanes in the presence of a metal catalyst (JP-A-4-334551, etc.), etc. Is mentioned.
  • Examples of the silazane of the component (A) include an average unit formula: (R 3 3 SiNR 4 ) a (R 3 2 SiNR 4 ) b (R 3 SiNR 4 ) c (SiNR 4 ) d (In the formula, each R 3 independently represents a crosslinkable group, a monovalent substituted or unsubstituted saturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, or a hydrogen atom.
  • the saturated aliphatic hydrocarbon group, aromatic hydrocarbon group, alkoxy group and halogen atom have the same meaning as defined for the silane.
  • the silazane can be prepared by methods well known in the art. For example, U.S. Pat.Nos. 4,321,970, 4,340,619, 4,395,460, 4,404,153, 4,482,689, 4,398,828, 4,540,343, 4,543,344, 4,835,312, No. 4,929,742 and No. 4,916,200. Furthermore, J. et al. Mater. Sci. 22, 2609 (1987).
  • Examples of the siloxane of the component (A) include an average unit formula: (R 3 3 SiO 1/2 ) a (R 3 2 SiO 2/2 ) b (R 3 SiO 3/2 ) c (SiO 4/2 ) d (In the formula, each R 3 independently represents a crosslinkable group, a monovalent substituted or unsubstituted saturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, or a hydrogen atom.
  • the saturated aliphatic hydrocarbon group, aromatic hydrocarbon group, alkoxy group and halogen atom have the same meaning as defined for the silane.
  • the siloxane can be prepared by methods well known in the art.
  • the method for preparing siloxane is not particularly limited. Most commonly, siloxanes are prepared by hydrolysis of organochlorosilanes. Such and other methods are described in Noll, Chemistry and Technology of Silicones, Chapter 5 (translated 2nd German version, Academic Press, 1968).
  • Examples of the carbosilane of the component (A) include an average unit formula: (R 3 3 SiCR 5 R 6 ) a (R 3 2 SiCR 5 R 6 ) b (R 3 SiCR 5 R 6 ) c (SiCR 5 R 6 ) d (In the formula, each R 3 independently represents a crosslinkable group, a monovalent substituted or unsubstituted saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group, an alkoxy group, or a hydrogen atom.
  • the saturated aliphatic hydrocarbon group, aromatic hydrocarbon group, alkoxy group and halogen atom have the same meaning as defined for the silane.
  • the carbosilane can be prepared by a method well known in the art.
  • the preparation method of carbosilane is described in, for example, Macromolecules, 21, 30 (1988), US Pat. No. 3,293,194.
  • silane, silazane, siloxane, and carbosilane is not particularly limited, and may be solid, liquid, paste, or the like, but is preferably solid in terms of handleability.
  • the silicon content is not extremely low, it has sufficient chemical stability, it is easy to handle at room temperature and in air, and the raw material price and manufacturing process cost are low enough.
  • a siloxane composed of units having a silicon-oxygen-silicon bond is preferred, and a polysiloxane is more preferred.
  • the component (A) may be one type of organic compound or a mixture of two or more types, and may further contain a nitrogen-containing monomer such as acrylonitrile as another component.
  • a nitrogen-containing monomer such as acrylonitrile
  • the content of the nitrogen-containing monomer is preferably 50% by mass or less, and particularly preferably in the range of 10 to 50% by mass.
  • the component (B) is a silicon-containing compound capable of crosslinking the component (A).
  • Examples of such component (B) include siloxane, silane, silazane, carbosilane, and mixtures thereof.
  • siloxanes such as monomers, oligomers, or polymers having a Si—O—Si bond; , Silanes such as monomers, oligomers or polymers having a Si—Si bond; silalkylenes such as monomers, oligomers or polymers having a Si— (CH 2 ) n —Si bond; Si— (C 6 H 4 ) n ⁇ Si or Si- (CH 2 CH 2 C 6 H 4 CH 2 CH 2) silarylene of monomers having n -Si bonds, oligomers or polymers; Si-n-Si monomer having a binding, such as oligomers or polymers Silazanes; Si—O—Si bond, Si—Si bond, Si— (CH 2 ) n —S
  • each R 7 independently represents a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acrylic group-containing organic group, a methacryl group-containing organic group, an amino group-containing organic group, or a mercapto group.
  • the monovalent hydrocarbon group for R 7 include an alkyl group, an alkenyl group, an aralkyl group, and an aryl group.
  • the alkyl group is preferably a C 1 to C 12 alkyl group, and particularly preferably a C 1 to C 6 alkyl group.
  • the alkyl group is a linear or branched alkyl group, a cycloalkyl group, or a cycloalkylene group (a linear or branched alkylene group (preferably a C 1 -C 6 alkylene group such as a methylene group or an ethylene group). ) And a carbon ring (preferably an alkyl group composed of a C 3 to C 8 ring).
  • the linear or branched alkyl group is preferably a linear or branched C 1 -C 6 alkyl group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, Examples are t-butyl group, pentyl group, and hexyl group.
  • the cycloalkyl group is preferably a C 4 to C 6 cycloalkyl group, and specific examples include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
  • the alkenyl group is preferably a C 2 to C 12 alkenyl group, and particularly preferably a C 2 to C 6 alkenyl group.
  • Specific examples of the C 2 -C 6 alkenyl group include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group, and a vinyl group is preferable.
  • the aralkyl group is preferably a C 7 to C 12 aralkyl group.
  • Specific examples of the C 7 to C 12 aralkyl group include a benzyl group, a phenethyl group, and phenylpropyl.
  • the aryl group is preferably a C 6 -C 12 aryl group, and specific examples thereof include a phenyl group, a naphthyl group, and a tolyl group. These monovalent hydrocarbon groups may have a substituent. Specific examples of the substituent include halogen such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; alkoxy group such as methoxy group, ethoxy group, n-propoxy group and isopropoxy group.
  • Such a substituted monovalent hydrocarbon group include a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, a perfluorobutylethyl group, and a perfluorooctylethyl group.
  • halogen atom for R 7 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
  • epoxy group-containing organic group represented by R 7 include glycidoxyalkyl groups such as 3-glycidoxypropyl group and 4-glycidoxybutyl group; 2- (3,4-epoxycyclohexyl). -An epoxy cyclohexyl alkyl group such as an ethyl group or a 3- (3,4-epoxycyclohexyl) -propyl group; an oxiranyl alkyl group such as a 4-oxiranylbutyl group or an 8-oxiranyloctyl group; A glycidoxyalkyl group is preferable, and a 3-glycidoxypropyl group is particularly preferable.
  • acrylic group-containing organic group or the methacrylic group-containing organic group represented by R 7 include a 3-acryloxypropyl group, a 3-methacryloxypropyl group, a 4-acryloxybutyl group, and a 4-methacryloxybutyl group. And is preferably a 3-methacryloxypropyl group.
  • amino group-containing organic group for R 7 examples include a 3-aminopropyl group, a 4-aminobutyl group, and an N- (2-aminoethyl) -3-aminopropyl group. 3-aminopropyl group and N- (2-aminoethyl) -3-aminopropyl group.
  • mercapto group-containing organic group for R 7 examples include a 3-mercaptopropyl group and a 4-mercaptobutyl group.
  • alkoxy group for R 7 examples include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group, and a methoxy group and an ethoxy group are preferable.
  • R 7 in one molecule is an alkenyl group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acrylic group-containing organic group, a methacryl group-containing organic group, or an amino group.
  • Such siloxanes are structural units represented by (R 7 3 SiO 1/2 ), (R 7 2 SiO 2/2 ), (R 7 SiO 3/2 ), and (SiO 4/2 ). It is composed of at least one unit of the, in particular, (R 7 3 SiO 1/2) and linear polysiloxane comprising units of (R 7 2 SiO 2/2); (R 7 2 Cyclic polysiloxane composed of units of (SiO 2/2 ); branched polysiloxane composed of units of (R 7 SiO 3/2 ) or (SiO 4/2 ); (R 7 3 SiO 1/2 ) and (R 7 SiO 3/2 ) units of polysiloxane; (R 7 3 SiO 1/2 ) and (SiO 4/2 ) units of polysiloxane; (R 7 SiO 3/2 ) and (SiO 4/2 ) ) Units of polysiloxane (R 7 2 SiO 2/2) and polysiloxane comprising units of (R 7 Si
  • the preferred number of repeating structural units represented by (R 7 3 SiO 1/2 ), (R 7 2 SiO 2/2 ), (R 7 SiO 3/2 ), and (SiO 4/2 ) is respectively It is preferably in the range of 1 to 10,000, more preferably in the range of 1 to 1,000, and particularly preferably in the range of 3 to 500.
  • siloxanes can be prepared by methods well known in the art.
  • the method for preparing the siloxanes is not particularly limited, and is most commonly prepared by hydrolysis of organochlorosilanes. Such and other methods are those described in Noll, Chemistry and Technology of Silicones, Chapter 5 (translated 2nd German version, Academic Press, 1968).
  • siloxanes may be silicon-containing copolymer compounds with polymers.
  • silicon-containing copolymer compound having Si—O—Si bond and Si—Si bond silicon-containing copolymer compound having Si—O—Si bond and Si—N—Si bond; Si—O—Si bond And Si- (CH 2 ) n —Si bond-containing copolymer compound; Si—O—Si bond and Si— (C 6 H 4 ) n —Si bond or Si— (CH 2 CH 2 C 6 H)
  • a silicon-containing copolymer compound having a 4 CH 2 CH 2 ) n —Si bond or the like can be used as the siloxane.
  • n is the same as described above.
  • Silanes are, for example, general formulas: R 7 4 Si Or average unit formula: (R 7 3 Si) a (R 7 2 Si) b (R 7 Si) c (Si) d (In the formula, each R 7 independently represents a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acrylic group-containing organic group, a methacryl group-containing organic group, an amino group-containing organic group, or a mercapto group.
  • silanes are represented by a general formula: R 7 4 Si or a structure represented by (R 7 3 Si), (R 7 2 Si), (R 7 Si), and (Si). It is composed of at least one unit among the units, specifically, a linear polysilane composed of units of (R 7 3 Si) and (R 7 2 Si); composed of units of (R 7 2 Si) Cyclic polysilane; Branched polysilane (polysilin) consisting of units of (R 7 Si) or (Si); Polysilane consisting of units of (R 7 3 Si) and (R 7 Si); (R 7 3 Si) and ( (Si) unit polysilane; (R 7 Si) and (Si) unit polysilane; (R 7 2 Si) and (R 7 Si) unit polysilane; (R 7 2 Si) and (Si) (R; polysilane consisting of units) 3 Si), (polysilane composed of units of R 7 2 Si) and (R 7 Si); (R 7 3 Si), (
  • the preferable number of repeating structural units represented by (R 7 3 Si), (R 7 2 Si), (R 7 Si) and (Si) is preferably in the range of 2 to 10,000, Is preferably within the range of 3 to 1,000, and particularly preferably within the range of 3 to 500.
  • silanes can be prepared using various known methods. For example, a method of dehalogenating a halosilane in the presence of an alkali metal (Macromolecules, 23, 3423 (1990), etc.), a method of anionic polymerization of disilene (Macromolecules, 23, 4494 (1990), etc.), electrode reduction, etc. (J. Chem. Soc., Chem. Commun., 1161 (1990), J. Chem. Soc., Chem.
  • silanes may be silicon-containing copolymer compounds with other polymers.
  • silanes have the general formula: [(R 8 ) 2 HSi] e R 9
  • R 8 is each independently a substituted or unsubstituted monovalent hydrocarbon group
  • e is an integer of 2 or more
  • R 9 is an e-valent organic group.
  • Silicon compounds are exemplified.
  • examples of the monovalent hydrocarbon group for R 8 include the same groups as the monovalent hydrocarbon group for R 7 .
  • e is an integer of 2 or more, preferably an integer of 2 to 6.
  • R 9 is an e-valent organic group, and when e is 2, R 9 is a divalent organic group.
  • R 9 is a trivalent organic group, and specific examples thereof include the following groups.
  • silazanes include, for example, an average unit formula: (R 7 3 SiNR 10 ) a (R 7 2 SiNR 10 ) b (R 7 SiNR 10 ) c (SiNR 10 ) d (In the formula, each R 7 independently represents a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acrylic group-containing organic group, a methacryl group-containing organic group, an amino group-containing organic group, or a mercapto group.
  • R 7 in one molecule is an alkenyl group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acrylic group A group-containing organic group, a methacryl group-containing organic group, an amino group-containing organic group, a mercapto group-containing organic group, an alkoxy group or a hydroxy group;
  • R 10 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group;
  • Examples of the monovalent hydrocarbon group for R 10 include the same groups as the monovalent hydrocarbon group for R 7 .
  • R 10 is preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a methyl group.
  • This silazane is composed of at least one unit among structural units represented by (R 7 3 SiNR 10 ), (R 7 2 SiNR 10 ), (R 7 SiNR 10 ), and (SiNR 10 ).
  • a linear polysilazane composed of units of (R 7 3 SiNR 10 ) and (R 7 2 SiNR 10 ); a cyclic polysilazane composed of units of (R 7 2 SiNR 10 ); (R 7 SiNR 10 ) Or (SiNR 10 ) units of branched polysilazane; (R 7 3 SiNR 10 ) and (R 7 SiNR 10 ) units of polysilazane; (R 7 3 SiNR 10 ) and (SiNR 10 ) units A polysilazane comprising units of (R 7 SiNR 10 ) and (SiNR 10 ); (R 7 2 SiNR 10 ) and (R 7 SiNR 10 ) units; polysilazane (R 7 2 SiNR 10 ) and (SiNR 10 ) units;
  • the preferred number of repeating structural units represented by (R 7 3 SiNR 10 ), (R 7 2 SiNR 10 ), (R 7 SiNR 10 ), and (SiNR 10 ) is in the range of 2 to 10,000, respectively. More preferably, it is preferably within the range of 3 to 1,000, and particularly preferably within the range of 3 to 500.
  • silazanes can be prepared by methods well known in the art. Methods for preparing such silazanes include, for example, U.S. Pat. Nos. 4,321,970, 4,340,619, 4,395,460, 4,404,153, 4,482,689, 4,398,828, 4,540,803, 4,543,344, 4,835,238, No. 4,774,312, No. 4,929,742 and No. 4,916,200. Furthermore, J. et al. Mater. Sci. 22, 2609 (1987).
  • silazanes may be silicon-containing copolymer compounds with other polymers.
  • silicon-containing copolymer compound having Si—N—Si bond and Si—O—Si bond; silicon-containing copolymer compound having Si—N—Si bond and Si—Si bond; Si—N—Si bond and Si- (CH 2) containing copolymer compounds having n -Si bonds; Si-n-Si bonds and Si- (C 6 H 4) n -Si bonds or Si- (CH 2 CH 2 C 6 H 4 CH 2 CH 2) n containing copolymer compounds having -Si bond or the like may be used as a polysilazane.
  • n is the same as described above.
  • carbosilanes include an average unit formula: (R 7 3 SiR 11 ) a (R 7 2 SiR 11 ) b (R 7 SiR 11 ) c (SiR 7 ) d (In the formula, each R 7 independently represents a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acrylic group-containing organic group, a methacryl group-containing organic group, an amino group-containing organic group, or a mercapto group.
  • R 7 in one molecule is an alkenyl group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acrylic group A group-containing organic group, a methacryl group-containing organic group, an amino group-containing organic group, a mercapto group-containing organic group, an alkoxy group, or a hydroxy group;
  • the alkylene group of R 11 is represented by, for example, the formula: — (CH 2 ) n —, and the arylene group of R 5 is represented, for example, by the formula: — (C 6 H 4 ) n —.
  • n is the same as described above.
  • the carbosilanes are composed of at least one of structural units represented by (R 7 3 SiR 11 ), (R 7 2 SiR 11 ), (R 7 SiR 11 ), and (SiR 11 ), Specifically, for example, a linear polycarbosilane composed of units of (R 7 3 SiR 11 ) and (R 7 2 SiR 11 ); a cyclic polycarbosilane composed of units of (R 7 2 SiR 11 ); R 7 SiR 11 ) or branched polycarbosilane composed of (SiR 11 ) units; (R 7 3 SiR 11 ) and (R 7 SiR 11 ) units composed of units; (R 7 3 SiR 11 ) and polycarbosilane comprising units of (SiR 11); (R 7 SiR 11) and polycarbosilane comprising units of (SiR 11); (R 7 2 SiR 1) and (polycarbosilane consisting R 7 SiR 11) units; (R 7 2 SiR 11
  • the preferable number of repeating structural units represented by (R 7 3 SiR 11 ), (R 7 2 SiR 11 ), (R 7 SiR 11 ) and (SiR 11 ) is within the range of 2 to 10,000, respectively. More preferably, it is preferably within the range of 3 to 1,000, and particularly preferably within the range of 3 to 500.
  • carbosilanes can be prepared by methods well known in the art. The method for preparing carbosilanes is described in, for example, Macromolecules, 21, 30 (1988), US Pat. No. 3,293,194.
  • These carbosilanes may be silicon-containing copolymer compounds with other polymers.
  • a silicon-containing copolymer compound having a Si— (CH 2 ) n —Si bond and a Si—O—Si bond a silicon-containing copolymer having a Si— (CH 2 ) n —Si bond and a Si—Si bond Compound; silicon-containing copolymer compound having Si— (CH 2 ) n —Si bond and Si—N—Si bond; Si— (CH 2 ) n —Si bond and Si— (C 6 H 4 ) n —Si Silicon-containing copolymer compound having a bond; silicon-containing copolymer compound having a Si— (C 6 H 4 ) n —Si bond and a Si—O—Si bond; Si— (C 6 H 4 ) n —Si bond And a silicon-containing copolymer compound having a Si—Si bond; Si— (C 6 H
  • each R 7 independently represents a monovalent hydrocarbon group, a hydrogen atom, a halogen atom, an epoxy group-containing organic group, an acrylic group-containing organic group, a methacryl group-containing organic group, an amino group-containing organic group, or a mercapto group.
  • crosslinking reactions include hydrosilylation reactions, Michael addition reactions, Diels-Alder reactions, and the like; condensation reactions such as dealcoholization, dehydrogenation, dehydration, and deamination; epoxy ring opening, ester ring opening, etc. Ring-opening reaction; radical reactions such as peroxide and UV are exemplified.
  • the hydrosilylation reaction can be performed in the presence of a hydrosilylation reaction catalyst.
  • hydrosilylation reaction catalyst examples include platinum fine powder, platinum black, platinum-supported silica fine powder, platinum-supported activated carbon, chloroplatinic acid, platinum tetrachloride, chloroplatinic acid alcohol solution, platinum and olefins.
  • Complexes, platinum and alkenylsiloxane complexes are exemplified.
  • the content is not particularly limited, but the metal atoms in the catalyst are within the range of 0.1 to 1,000 ppm in terms of mass (weight) with respect to the total amount of the components (A) and (B). It is preferable that the amount be in the range of 1 to 500 ppm.
  • the component (A) has an aliphatic unsaturated group and the component (B) has a silicon-bonded hydrogen atom
  • the component (A) has a silicon-bonded hydrogen atom
  • the component (B) When A has an aliphatic unsaturated group, the amount of each component used is not particularly limited, but the component (B) or (A )
  • the amount of silicon-bonded hydrogen atoms in the component is in the range of 0.1 to 50 mol, preferably in the range of 0.1 to 30 mol, particularly preferably 0.1 The amount is in the range of ⁇ 10 mol.
  • the component (A) has an aliphatic unsaturated group
  • the component (B) has an aliphatic unsaturated group, an acrylic group, a methacryl group, or a silicon-bonded hydrogen atom
  • the component (B) In the case where the component (A) has an aliphatic unsaturated group, an acrylic group, a methacryl group, or a silicon atom-bonded hydrogen atom, it undergoes a radical reaction by heat and / or light with a radical initiator. You can also.
  • radical initiator examples include organic peroxides such as dialkyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate, and organic azo compounds.
  • organic peroxides such as dialkyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate, and organic azo compounds.
  • dibenzoyl peroxide bis-p-chlorobenzoyl peroxide, bis-2,4-dichlorobenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl perbenzoate, 2,5-bis (t-butylperoxy) -2,3-dimethylhexane, t-butyl peracetate, bis (o-methylbenzoyl peroxide), bis (m-methylbenzoyl peroxide) ), Bis (p-methylbenzoyl peroxide), 2,3-dimethylbenzoyl peroxide, 2,4-dimethyl
  • organic azo compound examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis).
  • examples include (2,4-dimethylvaleronitrile), 2,2′-azobis-isobutylvaleronitrile, and 1,1′-azobis (1-cyclohexanecarbonitrile).
  • the content of the radical initiator is not particularly limited, but is preferably an amount that falls within a range of 0.1 to 10 mass (weight)% with respect to the total amount of the component (A) and the component (B). In particular, the amount is preferably in the range of 0.5 to 5 mass (weight)%.
  • the component (A) has an aliphatic unsaturated group
  • the component (B) has an aliphatic unsaturated group, an acrylic group, a methacryl group, or a silicon atom-bonded hydrogen atom
  • the component (B) When it has an aliphatic unsaturated group and the component (A) has an aliphatic unsaturated group, an acrylic group, a methacryl group or a silicon atom-bonded hydrogen atom, the amount of each component used is not particularly limited, The amount of the aliphatic unsaturated group, acrylic group, methacrylic group or silicon atom-bonded hydrogen atom in the other component in the range of 0.1 to 50 moles per mole of the aliphatic unsaturated group of The amount is preferably in the range of 0.1 to 30 mol, and particularly preferably in the range of 0.1 to 10 mol.
  • a lithium-coated metal silicon or silicon alloy fine powder is mixed with the component (A) and the component (B) to form a cured product obtained by crosslinking the components (A) and (B), for example, the following I or It can manufacture by the method of II, and can move to the process of heat processing (baking) then.
  • the obtained cured product may be used as it is in the next baking step, or may be used in the next baking step after being pulverized to a particle size of 0.1 to 30 ⁇ m, more preferably 1 to 20 ⁇ m.
  • the cured product is formed as spherical particles, for example, is a crosslinkable composition formed by spraying a crosslinkable composition comprising lithium-coated silicon or silicon alloy fine powder, (A) component and (B) component in hot air?
  • a crosslinking reaction by emulsifying or dispersing in a medium incompatible with the crosslinkable composition.
  • the component (A) or the component (B) When one of the component (A) or the component (B) has an aliphatic unsaturated group and the other has a silicon atom-bonded hydrogen atom, the component (A), the component (B) and the hydrosilylation reaction catalyst are mixed.
  • the resulting crosslinkable composition is sprayed into hot air in the form of fine particles and crosslinked by a hydrosilylation reaction to obtain a fine particle cured product powder.
  • the crosslinkable composition obtained by mixing the component (A), the component (B) and the hydrosilylation reaction catalyst is added to an aqueous solution of an emulsifier, and emulsified by stirring to form fine particles of the crosslinkable composition. Subsequently, it can also be crosslinked by a hydrosilylation reaction to form a fine particle cured product powder.
  • This emulsifier is not particularly limited, and specific examples include ionic surfactants, nonionic surfactants, and mixtures of ionic surfactants and nonionic surfactants.
  • ionic surfactants since the uniform dispersibility and stability of the oil-in-water emulsion produced by mixing the crosslinkable composition and water are good, one or more ionic surfactants and one or more nonionics are used. It is preferred to use a mixture of surfactants.
  • a metal oxide such as silica (colloidal silica) or titanium oxide in combination with an emulsifier
  • carbonization is performed while holding the silica on the surface of the cured powder, thereby forming a stable film on the carbon surface. Further, it is possible to increase the carbonization yield or to suppress surface oxidation that occurs when the carbon material is left standing.
  • the particle size of the cured product powder is not particularly limited, but since a composite material having an average particle size of 1 to 20 ⁇ m suitable as an electrode active material is formed by firing, the preferable average particle size is in the range of 5 to 30 ⁇ m. It is particularly preferable that the thickness is in the range of 5 to 20 ⁇ m.
  • the composite material of the present invention can be obtained through a step of heat-treating (baking) a cured product containing the component (A) and the component (B).
  • the firing conditions are not particularly limited, but firing at 300 to 1500 ° C. in an inert gas or vacuum is preferable. Nitrogen, helium, and argon are illustrated as an inert gas.
  • the inert gas may contain a reducing gas such as hydrogen gas.
  • the firing temperature is more preferably in the range of 500 ° C to 1000 ° C.
  • the firing time is not particularly limited, but can be, for example, in the range of 10 minutes to 10 hours, preferably 30 minutes to 3 hours.
  • Calcination can be performed in a fixed bed or fluidized bed type carbonization furnace, and the heating method and type of the carbonization furnace are not particularly limited as long as the furnace has a function of raising the temperature to a predetermined temperature.
  • the carbonization furnace include a lead hammer furnace, a tunnel furnace, a single furnace, and an oxynon furnace.
  • the composite material of the present invention thus obtained is characterized in that metal silicon or silicon alloy fine powder having a lithium-containing layer on its surface is dispersed in silicon-containing carbon-based composite particles.
  • an electrode having a high initial discharge capacity and a reduced initial irreversible capacity can be obtained.
  • the silicon-containing carbon-based composite material preferably has an amorphous structure in which silicon atoms are bonded to oxygen atoms and carbon atoms. Such a structure can be confirmed by 29 Si MAS NMR or X-ray diffraction analysis. When the silicon-containing carbon-based composite material is crystallized, the charge / discharge cycle characteristics and the initial charge / discharge efficiency may be reduced.
  • the density of Si-C bonds of the silicon-containing carbon-based composite material at the interface between the metal silicon or silicon alloy fine powder and the silicon-containing carbon-based composite material that is the matrix is the metal silicon in the silicon-containing carbon-based composite material or It is preferably higher than the density of Si—C bonds other than the interface portion with the silicon alloy fine powder.
  • Such a structure is presumed to suppress the destruction of metal silicon or silicon alloy fine powder in the matrix.
  • Such a structure can be confirmed by a binding state mapping technique of TEM-EELS analysis.
  • the surface of the composite material of the present invention may be further subjected to a surface coating treatment with carbon.
  • the carbon surface coating method of the composite material is arbitrary.
  • the carbon film derived from the vapor deposition carbon source (D1) may be subjected to thermal chemical vapor deposition on the surface of the composite material at a temperature of 800 ° C. or higher in a non-oxidizing atmosphere.
  • the composite material covered with the carbon phase derived from the organic material carbonized by heat can also be obtained by mixing (D2) the organic material carbonized by heat and the composite material and further baking. Further, (D3) it is possible to coat the composite material surface with carbon black by applying mechanical energy.
  • the apparatus used for the thermal chemical vapor deposition is not particularly limited as long as it has an apparatus for heating to 800 ° C. or higher in a non-oxidizing atmosphere, and can be appropriately selected according to the purpose.
  • a continuous method, a batch method, and an apparatus using both of these can be used.
  • Specific examples include a fluidized bed reactor, a rotary furnace, a vertical moving bed reactor, a tunnel furnace, a batch furnace, a batch rotary kiln, and a continuous rotary kiln.
  • (D1) vapor deposition carbon source used in the thermal chemical vapor deposition treatment is an aliphatic hydrocarbon such as methane, ethane, ethylene, acetylene, propane, butane, butene, pentane, isobutane, hexane, or a mixture thereof.
  • Aromatic hydrocarbons such as benzene, divinylbenzene, monovinylbenzene, ethyl vinylbenzene, toluene, xylene, styrene, ethylbenzene, diphenylmethane, naphthalene, phenol, cresol, nitrobenzene, chlorobenzene, indene, coumarone, pyridine, anthracene, phenanthrene Gas gas oil, creosote oil, anthracene oil, naphtha cracked tar oil obtained in the tar distillation process; exhaust gas generated in the calcination process, or a mixture thereof. It is common to be methane or acetylene.
  • the non-oxidizing atmosphere includes the vapor deposition carbon source gas or a vaporized gas thereof; a non-oxidizing gas such as argon gas, helium gas, hydrogen gas, nitrogen gas; Can be obtained.
  • (D2) When the organic material carbonized by heat and the composite material are mixed and further baked to obtain a composite material covered with a carbon phase derived from the organic material carbonized by heat, baking is performed in the same manner as described above. Can be done.
  • organic materials that are carbonized by heat include paraffin, polyethylene, polypropylene, polystyrene, polymethyl methacrylate, urethane resin, AS resin, ABS resin, polyvinyl chloride, and polyacetal that are liquid or waxy at room temperature.
  • aromatic polycarbonate resins aromatic polyester resins, coal tar, phenol resins, epoxy resins, urea resins, melamine resins, fluororesins, imide resins, urethane resins, furan resins, and mixtures thereof.
  • high molecular weight aromatic compounds such as aromatic polycarbonates, aromatic polyesters, coal tars, phenol resins, fluororesins, imide resins, furan resins, and melamine resins are preferable. This is because the carbonization efficiency by heat is good, such as the formation of a graphene structure is easy.
  • the coating amount of carbon is preferably 1 to 50 mass (weight)%, more preferably 5 to 30 mass (weight)% in the composite material. More preferably, it is ⁇ 20 mass (weight)%. This is because even when only a composite material is used as the electrode active material, it has suitable conductivity and can suppress a decrease in charge / discharge capacity of the electrode.
  • the composite material of the present invention can be in the form of particles having an average particle diameter of 5 nm to 50 ⁇ m.
  • the average particle size is preferably 10 nm to 40 ⁇ m, more preferably 100 nm to 30 ⁇ m, and even more preferably 1 ⁇ m to 20 ⁇ m.
  • the composite material of the present invention can be used as an electrode active material.
  • the electrode active material of the present invention can be in the form of particles, in which case the average particle size is preferably 1 to 50 ⁇ m, more preferably 1 to 40 ⁇ m, and further preferably 1 to 30 ⁇ m. Is more preferable.
  • the electrode active material made of the composite material of the present invention has a high initial discharge capacity, and enables an electrode with reduced initial irreversible capacity (difference between initial charge capacity and initial discharge capacity) to be manufactured by a simple manufacturing process. be able to. Therefore, this electrode active material can be suitably used as an active material for an electrode of a nonaqueous electrolyte secondary battery. In particular, this electrode active material is suitable as an active material for electrodes of lithium or lithium ion secondary batteries.
  • the electrode of the present invention is characterized by containing the above electrode active material, and the shape and preparation method of the electrode are not particularly limited.
  • a method for preparing the electrode of the present invention specifically, a method in which a composite material is mixed with a binder to produce an electrode; the composite material is mixed with a binder and a solvent, and the resulting paste is placed on a current collector. Examples thereof include a method of producing an electrode by a method such as pressure bonding or coating on a current collector and then drying to form an electrode.
  • the thickness of the paste applied to the current collector is, for example, about 30 to 500 ⁇ m, preferably about 50 to 300 ⁇ m.
  • the means for drying after coating is not particularly limited, but a heat vacuum drying treatment is preferable.
  • the film thickness of the electrode material on the current collector after the drying treatment is, for example, about 10 to 300 ⁇ m, preferably about 20 to 200 ⁇ m.
  • an electrode is produced by arranging it in a uniaxial direction or in the form of a woven fabric or the like, and bundling or braiding with conductive fibers such as metal or conductive polymer. be able to. In forming the electrodes, terminals may be combined as necessary.
  • the current collector is not particularly limited, and specifically, a metal mesh or foil such as copper, nickel, or an alloy thereof is exemplified.
  • binders include fluorine resins (polyvinylidene fluoride, polytetrafluoroethylene, etc.), styrene-butadiene resins, carboxymethylcellulose, sodium carboxymethylcellulose, polyacrylic acid, sodium polyacrylate, polyimide, polyamide, styrene- Butadiene rubber is exemplified.
  • the amount of the binder used is not particularly limited, and the lower limit thereof is in the range of 5 to 30 mass (weight) parts, preferably 5 to 20 mass parts with respect to 100 mass (weight) parts of the composite material. It is within the range of mass (weight) part.
  • the method for preparing the paste is not particularly limited, and examples thereof include a method of mixing a composite material in a mixed liquid (or dispersion liquid) of a binder and an organic solvent.
  • a solvent capable of dissolving or dispersing the binder is usually used, and specific examples thereof include organic solvents such as N-methylpyrrolidone and N, N-dimethylformamide.
  • the amount of the solvent used is not particularly limited as long as it is in a paste form. For example, it is usually within a range of 0.01 to 500 mass (weight) parts, preferably 0.00. It is within the range of 01 to 400 parts by weight (weight), more preferably within the range of 0.01 to 300 parts by weight (weight).
  • the ratio of the conductive auxiliary agent is not particularly limited, but it is in the range of 2 to 60 mass (weight) parts, preferably in the range of 5 to 40 mass (weight) parts with respect to 100 mass (weight) parts of the composite material. More preferably, it is in the range of 5 to 20 parts by mass (weight). It is because it is excellent in electroconductivity and can suppress the fall of the charge / discharge capacity of an electrode.
  • Examples of the conductive aid include carbon black (Ketjen black, acetylene black, etc.), carbon fiber, carbon nanotube, and the like.
  • a conductive support agent can be used individually or in combination of 2 or more types.
  • a conductive support agent can be mixed with the paste containing a composite material, a binder, and a solvent, for example.
  • an electrode active material such as graphite may be blended in the electrode of the present invention as any other additive.
  • An electricity storage device includes the electrode.
  • Examples of such electricity storage devices include lithium primary batteries, lithium secondary batteries, lithium ion secondary batteries, capacitors, hybrid capacitors (redox capacitors), organic radical batteries, and dual carbon batteries, particularly lithium or lithium ion secondary batteries.
  • a battery is preferred.
  • Lithium ion secondary batteries use, for example, battery components such as a negative electrode comprising the above electrodes, a positive electrode capable of inserting and extracting lithium, an electrolyte solution, a separator, a current collector, a gasket, a sealing plate, a case, and the like. Can be manufactured.
  • a lithium secondary battery can be produced by a conventional method using battery components such as a positive electrode made of the electrode, a negative electrode made of metallic lithium, an electrolyte, a separator, a current collector, a gasket, a sealing plate, and a case. it can.
  • the lithium or lithium ion secondary battery which is a preferred embodiment of the battery of the present invention, will be described in detail with reference to FIGS.
  • FIG. 1 is a schematic exploded sectional view of a button-type battery which is a lithium ion secondary battery which is an example of the battery of the present invention.
  • a lithium ion secondary battery shown in FIG. 1 includes a cylindrical case 1 having a bottom surface with a top opening, a cylindrical gasket 2 having an inner periphery that is substantially the same size as the outer periphery of the case 1, a washer 3, a SUS plate 4, It consists of a current collector 5, a negative electrode 6 containing the composite material of the present invention as an electrode active material, a separator 7, a positive electrode 8, a current collector 9, and a sealing plate 10.
  • a washer 3 having a substantially ring shape slightly smaller than the inner periphery of the case 1 is accommodated, and the inner periphery of the case 1 is placed on the washer 3.
  • a SUS plate 4 having a substantially disk shape slightly smaller than that is placed.
  • a current collector 5 and a negative electrode 6 that are both substantially disk-shaped and slightly smaller than the inner circumference of the case 1 are disposed.
  • a separator 7 as a disk-shaped member having a size substantially the same as the inner periphery of the case 1 is placed, and the separator 7 is impregnated with an electrolytic solution.
  • the separator 7 may be composed of two or more disk-shaped members.
  • a positive electrode 8 having a size substantially equal to that of the negative electrode 6 and a current collector 9 having a size substantially equal to that of the current collector 5 are disposed on the separator 7, a positive electrode 8 having a size substantially equal to that of the negative electrode 6 and a current collector 9 having a size substantially equal to that of the current collector 5 are disposed.
  • the current collector 5 is made of foil, mesh, or the like made of metal such as copper or nickel
  • the current collector 9 is made of foil, mesh, or the like made of metal such as aluminum, and the negative electrode 6 and the positive electrode, respectively. 8 is in close contact with and integrated.
  • the gasket 2 is fitted to the wall surface of the case 1, and the bottom-opening bottomed cylindrical sealing plate 10 having an inner peripheral surface slightly larger in size than the gasket 2.
  • the inner peripheral surface is further fitted to the outer peripheral surface of the gasket 2.
  • the positive electrode 8 in the lithium ion secondary battery shown in FIG. 1 is not particularly limited, and can be composed of, for example, a positive electrode active material, a conductive additive, a binder, and the like.
  • the positive electrode active material include metal oxides such as LiCoO 2 , LiNiO 2 , and LiMn 2 O 4 , polyanionic oxides such as LiFePO 4 and Li 2 FeSiO 4 , and spinel-type LiMn 2 O 4. .
  • Examples of the conductive aid and binder are the same as described above.
  • FIG. 2 is a schematic exploded cross-sectional view of a button-type battery that is a lithium secondary battery that is an example of the battery of the present invention manufactured in the examples.
  • the lithium secondary battery shown in FIG. 2 includes a cylindrical case 1 having a bottom surface with a top opening, a cylindrical gasket 2 having an inner periphery substantially the same size as the outer periphery of the case 1, a washer 3, a SUS plate 4, and a metal. It consists of a negative electrode 6 made of lithium, a separator 7, a positive electrode 8 containing the composite material of the present invention as an electrode active material, a current collector 9 ′, and a sealing plate 10.
  • a washer 3 having a substantially ring shape that is slightly smaller than the inner periphery of the case 1 is accommodated.
  • a SUS plate 4 having a substantially disk shape with a slightly smaller size is placed on the SUS plate 4.
  • a negative electrode 6 having a substantially disk shape slightly smaller than the inner periphery of the case 1 is disposed on the negative electrode 6, a separator 7 as a disk-shaped member having a size substantially the same as the inner periphery of the case 1 is placed, and the separator 7 is impregnated with an electrolytic solution.
  • the separator 7 may be composed of two or more disk-shaped members.
  • the current collector 9 ′ is made of a foil, mesh, or the like made of a metal such as copper or nickel, and is in close contact with the positive electrode 8 so as to be integrated.
  • the gasket 2 is fitted to the wall surface of the case 1, and the inside of the bottom-opening bottomed cylindrical sealing plate 10 having an inner peripheral surface slightly larger in size than the gasket 2.
  • the peripheral surface is further fitted to the outer peripheral surface of the gasket 2.
  • the electrolytic solution contained in the lithium or lithium ion secondary battery shown in FIGS. 1 and 2 is not particularly limited, and known ones can be used.
  • a non-aqueous lithium or lithium ion secondary battery can be manufactured by using a solution obtained by dissolving an electrolyte in an organic solvent as the electrolytic solution.
  • the electrolyte for example, can be exemplified LiPF 6, LiClO 4, LiBF 4 , LiClF 4, LiAsF 6, LiSbF 6, LiAlO 4, LiAlCl 4, LiCl, lithium salt such as LiI.
  • organic solvent examples include carbonates (propylene carbonate, ethylene carbonate, diethyl carbonate, etc.), lactones ( ⁇ -butyrolactone, etc.), chain ethers (1,2-dimethoxyethane, dimethyl ether, diethyl ether, etc.), cyclic Ethers (tetrahydrofuran, 2-methyltetrahydrofuran, dioxolane, 4-methyldioxolane, etc.), sulfolanes (sulfolane, etc.), sulfoxides (dimethylsulfoxide, etc.), nitriles (acetonitrile, propionitrile, benzonitrile, etc.), amides Aprotic solvents such as (N, N-dimethylformamide, N, N-dimethylacetamide and the like) and polyoxyalkylene glycols (diethylene glycol and the like) can be exemplified.
  • carbonates propylene carbonate, ethylene carbonate, dieth
  • An organic solvent may be used independently and may be used as a 2 or more types of mixed solvent.
  • the electrolyte concentration is, for example, about 0.3 to 5 mol, preferably 0.5 to 3 mol, and more preferably about 0.8 to 1.5 mol with respect to 1 L of the electrolyte.
  • additives may be added to the electrolytic solution as necessary.
  • Preferred additives include, for example, halogenated carbonates such as fluoromethyl methyl carbonate, 4-fluoro-1,3-dioxilan-2-one or 4,5-difluoro-1,3-dioxolan-2-one; vinyl Examples of the carbonate include carbonates, methyl vinylene carbonate, ethyl vinylene carbonate, and 4-vinylethylene carbonate. These additives are blended for the purpose of suppressing the decomposition reaction of the electrolytic solution and improving the cycle life of the battery.
  • the concentration of these additives in the electrolytic solution is preferably in the range of 0.1 to 50% by weight.
  • the separators 4 and 12 in the lithium or lithium ion secondary battery shown in FIG. 1 and FIG. 2 are not particularly limited, and are known separators such as polyolefin-based polyolefins such as porous polypropylene nonwoven fabric and porous polyethylene nonwoven fabric. A porous film or the like can be used.
  • the electricity storage device of the present invention is not limited to the examples shown in FIGS. 1 and 2, and may be various forms such as a laminated shape, a pack shape, a button shape, a gum shape, an assembled battery shape, and a square shape. Applicable.
  • the devices of the present invention particularly lithium or lithium ion secondary batteries, are lightweight and have high capacity and high energy density, so that they can be used in small portable devices such as video cameras, personal computers, word processors, radio cassettes, and mobile phones. It is preferably used as a power source for electronic devices, a power source for hybrid vehicles and electric vehicles, and a power storage power source.
  • the charge / discharge characteristics of the lithium ion secondary battery using the composite material of the present invention were measured as follows using HJR-110mSM6 manufactured by Hokuto Denko. Both the first charge and discharge were performed at a constant current of 0.1 C (37.2 mAh / g) per gram of the composite material, which was 1/10 of the theoretical capacity of 372 mAh / g of graphite. The first charge was completed when the battery voltage dropped to 0 V, and the initial charge capacity (mAh / g) was determined. The first discharge was completed when the battery voltage reached 3 V, and the initial discharge capacity (mAh / g) was determined. When switching between charge and discharge, it was left in an open circuit for 30 minutes.
  • the initial charge / discharge efficiency (CE%) is the percentage (%) of the initial discharge capacity with respect to the initial charge capacity
  • the capacity maintenance ratio after the cycle test is the percentage (%) of the discharge capacity after a predetermined cycle with respect to the discharge capacity at the second cycle. It was.
  • Preparation Example 1 (Preparation of silicon fine powder 1) In a solution obtained by dissolving 0.5 g of LiOH.H 2 O in 5 g of distilled water, 4.5 g of metal silicon fine powder (high-purity metal silicon for semiconductors manufactured by Dow Corning Co., Ltd., 9.99999% or more, (Average particle size, 1 ⁇ m) was added, and the mixture was stirred for 24 hours in a nitrogen atmosphere, and then dried by heating at 350 ° C. to obtain brown lithium surface-treated silicon fine powder (silicon fine powder 1).
  • metal silicon fine powder high-purity metal silicon for semiconductors manufactured by Dow Corning Co., Ltd., 9.99999% or more
  • the powder was pulverized to a fine powder having an average particle size of about 1 ⁇ m by a ball mill and a bead mill as a dispersion medium.
  • the obtained suspension was filtered, and after removing the solvent under a nitrogen atmosphere, the coarse particles were cut with an air precision classifier manufactured by Nissin Engineering Co., Ltd. to obtain a powder having an average particle size of about 0.8 ⁇ m. It was. Under a nitrogen atmosphere, 0.5 g of LiOH.H 2 O was added to 4.5 g of powder, and this mixture was milled for 5 minutes with a Millcer Mill MM301 ball mill apparatus manufactured by Lecce Co., Ltd. The powder was removed under a nitrogen atmosphere.
  • a treated silicon fine powder (silicon fine powder 3) was obtained.
  • X-ray diffraction (CuK ⁇ ) of this fine powder a specific diffraction peak derived from the Li—O—Si structure is observed in the vicinity of 2 ⁇ of 21 ° -22 °, 26 ° -27 °, 36 ° -37 °. It was.
  • [Preparation Example 4] (Preparation of silicon fine powder 4) To an aqueous solution in which 6.8 g of methyltrimethoxysilane was dissolved in 25 g of distilled water, 2.5 g of LiOH.H 2 O was added dropwise with stirring at 50 ° C., and concentrated to obtain an aqueous solution containing 20% by mass of lithium methyl silicate. .
  • DVB570 manufactured by Nippon Steel Chemical Co., Ltd., which is
  • the obtained crosslinkable composition is precured at 120 ° C., held in a muffle furnace with a temperature program capable of controlling the atmosphere in a nitrogen atmosphere at 600 ° C. for 2 hours, and further held at 1,000 ° C. for 1 hour. Firing was performed under the conditions, and pulverization and classification were performed to obtain a silicon-containing carbon-based composite material powder 1 having an average particle size of about 10 ⁇ m.
  • a block-shaped cured product obtained by curing the crosslinkable composition at 120 ° C. is placed in an alumina container with a lid, and is heated at 600 ° C. in a muffle furnace with a temperature program capable of controlling the atmosphere in a nitrogen atmosphere. After holding for a period of time, firing was further performed under the condition of holding at 1,000 ° C. for 1 hour. After cooling, the mixture was pulverized with a pulverizer (mass colloider) having a clearance of 20 ⁇ m to obtain a silicon-containing carbon-based composite material powder having an average particle size of about 10 ⁇ m and dispersed with fine lithium-coated metal silicon powder.
  • a pulverizer mass colloider
  • TGA analysis revealed that the content of zero-valent silicon fine powder in the silicon-containing carbon composite powder in which lithium-coated metal silicon fine powder was dispersed was 37.9% by mass. From TEM observation, it was confirmed that the silicon fine powder was dispersed in the silicon-containing carbon-based composite material.
  • TEM-EELS combining electron energy loss spectroscopy (Electron Energy-Loss Spectroscopy: EELS) with a transmission electron microscope, an energy loss peak is observed around 63 eV on the silicon fine powder surface in the silicon-containing carbon-based composite material. , Li was confirmed to be present.
  • the bonding state mapping method of the TEM-EELS analysis the density of Si-C bonds at the interface between the metal silicon fine powder and the silicon-containing carbon-based composite material that is the matrix is the matrix (silicon-containing carbon-based composite material). It was found that the density of Si—C bonds in the medium was extremely high.
  • a 85% by mass of silicon-containing carbon-based composite material in which the lithium-coated metal silicon fine powder prepared above was dispersed and 5% by mass of carbon black were added and mixed for 15 minutes. Then, 5% by mass of polyvinylidene fluoride-containing N-methyl-2-pyrrolidone solution is added so that the polyvinylidene fluoride is 10% by mass as solids, and an appropriate amount of N-methyl-2-pyrrolidone is added and mixed for 15 minutes. To make a slurry. Then, the slurry was apply
  • Example 2 A silicon-containing carbon-based composite powder in which lithium-coated metal silicon fine powder was dispersed was obtained in the same manner as in Example 1 except that the silicon fine powder 2 prepared in Preparation Example 2 was used instead of the silicon fine powder 1. .
  • Example 1 Using the silicon-containing carbon-based composite material in which the lithium-coated metal silicon fine powder prepared above was dispersed, an electrode was produced in the same manner as in Example 1, and a lithium ion secondary battery was produced and evaluated. Table 1 shows the battery characteristics.
  • Example 3 2.4 g of fine silicon powder 3 prepared in Preparation Example 3 above, 30 g of diphenylbis (dimethylvinylsiloxy) silane (containing 14.06% by mass vinyl group), and a methyl chain-blocked methyl at both ends of the molecular chain having a viscosity of 20 mPa ⁇ s.
  • a crosslinkable composition was prepared by mixing 10 ppm with a dental mixer using platinum catalyst as a platinum metal and a platinum catalyst of 1,3-divinyltetramethyldisiloxane complex in an amount of 1 mole of bonded hydrogen atoms). Thereafter, this composition was cured at 150 ° C. in nitrogen to prepare a cured product.
  • the SSA-S grade alumina boat was charged with 2.2 g of the fired product obtained after pulverization and classification, and the boat was placed in a muffle furnace. The inside of the muffle furnace was maintained at a reduced pressure for 60 minutes, and then returned to normal pressure with high-purity nitrogen (99.99%). This operation was repeated once in total. Thereafter, while supplying high-purity argon at a flow rate of 100 mL / min, the temperature was increased at a rate of 5 ° C./min, and baked at 1000 ° C. for 1 hour to obtain a silicon-containing carbon material.
  • TGA analysis revealed that the content of zero-valent silicon fine powder in the silicon-containing carbon-based composite material powder in which lithium-coated metal silicon fine powder was dispersed was 10.0% by mass.
  • Example 1 Using the silicon-containing carbon-based composite material in which the lithium-coated metal silicon fine powder prepared above was dispersed, an electrode was produced in the same manner as in Example 1, and a lithium ion secondary battery was produced and evaluated. Table 1 shows the battery characteristics.
  • a crosslinkable composition was prepared by mixing 10 ppm of platinum catalyst as platinum metal with an amount of about 1 mole of silicon-bonded hydrogen atoms in the resin and platinum catalyst of 1,3-divinylte
  • a block-shaped cured product obtained by curing the crosslinkable composition at 200 ° C. is placed in an alumina container with a lid, and is heated at 600 ° C. in a muffle furnace with a temperature program capable of controlling the atmosphere in a nitrogen atmosphere. After holding for a period of time, firing was further performed under the condition of holding at 1,000 ° C. for 1 hour. After cooling, the mixture was pulverized with a pulverizer (mass colloider) having a clearance of 20 ⁇ m to obtain a silicon-containing carbon-based composite material powder having an average particle size of about 10 ⁇ m and dispersed with fine lithium-coated metal silicon powder.
  • a pulverizer mass colloider
  • TGA analysis revealed that the content of zero-valent silicon fine powder in the silicon-containing carbon-based composite material powder in which lithium-coated metal silicon fine powder was dispersed was 80.0% by mass.
  • Example 1 Using the silicon-containing carbon-based composite material in which the lithium-coated metal silicon fine powder prepared above was dispersed, an electrode was produced in the same manner as in Example 1, and a lithium ion secondary battery was produced and evaluated. Table 1 shows the battery characteristics.
  • Example 1 A silicon-containing carbon-based composite material powder in which metal silicon fine powder was dispersed was obtained in the same manner as in Example 1 except that 1.5 g of metal silicon powder manufactured by Dow Corning Co., Ltd. was used instead of silicon fine powder 1. .
  • An electrode was produced in the same manner as in Example 1 using the obtained silicon-containing carbon-based composite powder in which the metal silicon fine powder was dispersed as an active material, and a lithium ion secondary battery was produced and evaluated. Table 1 shows the battery characteristics.
  • the initial charge / discharge efficiency (CE%) was significantly reduced, and the capacity retention rate was also reduced.
  • Example 3 An electrode was prepared in the same manner as in Example 1 using the silicon-containing carbon-based composite powder 1 prepared in Preparation Example 5 as an active material, and a lithium ion secondary battery was prepared and evaluated. Table 1 shows the battery characteristics.
  • the electrode active material of the present invention has reduced initial irreversible capacity (difference between initial charge capacity and initial discharge capacity), high initial discharge capacity, and stable charge / discharge cycle characteristics, It is particularly suitable for an electrode of a lithium or lithium ion secondary battery. Moreover, the electrode active material of the present invention can be manufactured by a simple manufacturing process using inexpensive raw materials. The electrode of the present invention can impart a high initial discharge capacity and stable charge / discharge cycle characteristics to the battery. Therefore, the electricity storage device of the present invention has an initial irreversible capacity reduced, a high initial discharge capacity, and stable charge / discharge cycle characteristics.

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Abstract

La présente invention a trait à un matériau composite dans lequel de particules fines d'alliage au silicium ou de métal au silicium, chacune d'entre elles étant dotée d'une couche contenant du lithium sur la surface, sont dispersées dans un matériau composite à base de carbone contenant du silicium. Le matériau composite peut être produit au moyen d'un procédé de production qui comprend : une première étape au cours de laquelle des particules fines d'alliage au silicium ou de métal au silicium revêtues de lithium sont obtenues en formant une couche contenant du lithium sur la surface de chaque particule d'alliage au silicium ou de métal au silicium ; une deuxième étape au cours de laquelle les particules fines d'alliage au silicium ou de métal au silicium revêtues de lithium sont mélangées avec (A) un composé organique contenant un groupe réticulable et (B) un composé contenant du silicium qui est réticulable avec le composé organique contenant un groupe réticulable, de sorte qu'un produit traité est obtenu au moyen d'une réaction de réticulation entre le composant (A) et le composant (B) ; et une troisième étape au cours de laquelle le produit traité est soumis à un traitement thermique. Le matériau composite est approprié pour les électrodes de dispositifs de stockage d'électricité, tout particulièrement les électrodes de batteries rechargeables au lithium ou au lithium-ion.
PCT/JP2012/066098 2011-06-27 2012-06-18 Matériau composite à base de carbone contenant du silicium dans lequel des particules fines d'alliage au silicium ou de métal au silicium revêtues de lithium sont dispersées Ceased WO2013002157A1 (fr)

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CN110931711A (zh) * 2018-09-19 2020-03-27 国家能源投资集团有限责任公司 锂金属负极及其制备方法和锂金属电池
CN110931711B (zh) * 2018-09-19 2021-03-09 国家能源投资集团有限责任公司 锂金属负极及其制备方法和锂金属电池

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